Methylthiomethyl esters as flavor additives

ABSTRACT

Methylthiomethyl esters of aliphatic acids have been found useful in imparting or enhancing flavors in foodstuffs. They are particularly useful with respect to fruit and berry flavors.

This application is a continuation-in-part of our copending applicationSer. No. 52,154, filed June 26, 1979, and now abandoned.

This invention relates to the use of methylthiomethyl esters ofaliphatic acids as flavor additives and to flavoring compositions andfoodstuffs containing such compounds.

Food scientists and researches are constantly striving to improve orstrengthen the flavor and the flavor impact of foodstuffs by use offlavor additives to replace flavor lost by the processing or in storageor to impart a "natural" flavor effect to a reconstituted foodstuff.Considerable effort is also being put into developing flavor compoundsand flavoring compositions for imparting flavors to otherwise bland ortasteless, though nutritionally useful, materials.

In accordance with this invention, there are provided flavoringcompositions or flavor enhancing compositions containingmethylthiomethyl esters of aliphatic acids, represented by thestructural formula R--COOCH₂ SCH₃ wherein R is selected from the groupconsisting of hydrogen, alkyl radicals with 1 to 9 carbon atoms, alkenylradicals with 2 to 9 carbon atoms and polyunsaturated alkyl radicalswith 4 to 9 carbon atoms. When R represents one of the above describedalkyl groups, the alkyl group can be straight-chain or branched-chain.Some of the compounds presented in this invention exist in isomericforms, and the compounds given herein include such isomers and mixturesthereof.

Although some of the compounds used in the present invention are knownin literature, there is no disclosure in the prior art indicating thatthey possess flavoring properties. The following methylthiomethyl estersof the aliphatic series are known from the chemical literature: theacetate, the propionate, the octanoate, the acrylate, and themethacrylate (see e.g., Chem. Abstr., 83, 192168U, Tetrah. Letters,1972, 4941-4, J. Amer. Chem. Soc., 92, 6521-5 (1970), Tetrahedron, 19,817-20 (1963), Can. J. Chem. 42, 2357-62 (1964), Chem. Abstr., 59,3806g, Ann., 626, 19-25 (1959), Syn. Comm., 3, 145-6 (1973), J.C.S.Chem. Comm., 1973, 224-5, Chem. Abstr., 72, 54677f, and J. Amer. Chem.Soc., 91, 682-7 (1969)).

As stated, the methylthiomethyl esters of this invention exhibit a widevariety of flavor effects giving rise to a wide field of uses. Inparticular, they are useful in fruit flavors, e.g., pineapple,strawberry, raspberry, blackcurrant, mango, durian, grape, apple, peach,pear, and other fruit and berry flavors. The esters are also useful incheese, cream, milk, meat, and vegetable flavors.

The following table illustrates some of the great variety of flavoreffects exhibited by the compounds presented in the invention.

    ______________________________________                                        Methylthiomethyl ester of                                                                      Organoleptic property                                        ______________________________________                                        formic acid      cabbage, meaty, onion, metallic                              acetic acid      estery, milky, cabbage, meat,                                                 sulfury                                                      propionic acid   dairy-like, yoghurt, sulfury                                 butyric acid     cabbage, milky, cheese                                       isobutyric acid  strawberry, pineapple                                        2-methylbutyric acid                                                                           fruity, strawberry, pineapple,                                                mango, durian                                                valeric acid     fruity, cheese, milky                                        isovaleric acid  blackcurrant, tropical fruits                                hexanoic acid    pineapple, fruity                                            heptanoic acid   fruity, pineapple, pear                                      octanoic acid    dairy-like, fruity, cheese                                   tiglic acid      sweet apple, fruity                                          2-hexenoic acid  green, cream, earthy, fatty                                  2-methyl-2-pentenoic acid                                                                      fruity, pear, sulfury                                        geranic acid     aldehydic, fruity, estery                                    citronellic acid aldehydic, wine, earthy                                      lavandulic acid  grape, radish, cabbage                                       ______________________________________                                    

The methylthiomethyl esters of this invention can be employed singly orin admixture of two or more. They all can be employed as componentseither of flavoring compositions or of flavor-enhancing compositions.

A flavoring composition means a combination of ingredients compounded tosupply or impart a specific flavor character to an otherwise blandingestible material, or to completely change an existing flavor. Aflavor-enhancing composition is a combination of ingredients which, incombination, are capable of reinforcing one or more flavor notes of anatural or other foodstuff to improve, supplement or augment a flavorwhich has been undesirably diminished or otherwise altered by processingor which is inferior due to the general quality of the foodstuffinitially. Either type of composition is usually suspended or dissolvedin an organoleptically inert carrier, although this is not absolutelynecessary.

When used in fruit or berry flavoring compositions, additional flavoringcompounds typically used in combination with the methylthiomethyl estersof the invention include, e.g.

    ______________________________________                                        orange oil        isoamyl acetate                                             phenyl ethyl isovalerate                                                                        fusel oil                                                   damascenone       lie de vin                                                  ethyl maltol      2-methyl butanol                                            2-methylbutyric acid                                                                            phenylethyl alcohol                                         angelica root oil trans-2-hexenol                                             buchu oil         methyl anthranilate                                         cognac oil        2-methyl-2-pentenoic acid                                   petitgrain oil    vanillin                                                    cedar leaf oil    maltol                                                      isoamyl isovalerate                                                                             benzyl alcohol                                              methyl butyrate   linaolool                                                   isobutyl acetate  isoamyl butyrate                                            methyl isobutyl carbinyl                                                                        ethyl acetate                                               acetate           ethyl butyrate                                              ethyl benzoate    ethyl hexanoate                                             citral            ethyl heptanoate                                            cuminic aldehyde  cis-3-hexenol                                               beta-ionone       ethyl isovalerate                                           tangerine oil     phenyl butyrate                                             benzyl acetate    amyl acetate                                                orange peel oil   geranyl acetate                                             bergamot oil      gamma-nonalactone                                           lime oil          Ylang Ylang                                                 orange terpenes   beta-terpineol                                              methyl cinnamate                                                              ______________________________________                                    

When used in dairy type flavors-i.e., cheese, butter, or cream flavors,additional flavoring compositions typically used in combination with themethylthiomethyl esters of the invention include:

    ______________________________________                                        delta-decalactone 2-heptanone                                                 heliotropin       gamma-undecalactone                                         butyric acid      ethyl lactate                                               hexanoic acid     gamma-decalactone                                           isovaleric acid   acetoin                                                     octanoic acid     diacetyl                                                    ______________________________________                                    

The term "foodstuff" includes both solid and liquid ingestible materialswhich usually do, but need not, have nutritional value. Thus, foodstuffsinclude fruit juices, fruit flavored beverages, puddings, jellies,pastries, ice cream, candies, chewing gum, dairy products, vegetables,cereals, meats, soups, convenience foods and the like. They can also beemployed to restore the fresh fruit effect of canned and frozen fruits.

The amount of methylthiomethyl ester added to a foodstuff needs to beonly the amount sufficient to impart or to enhance the desired flavor.Small amounts are effective, though the amount can be varied over a widerange depending upon the flavor strength required. Generally, the amountwill be between about 0.1 to 5 parts per million by weight based on thefoodstuff being flavored.

To prepare the methylthiomethyl esters described in this invention, thecorresponding acid is reacted with chloromethyl methyl sulfide in thepresence of one equivalent of an amine, for example, triethylamine (T.L. Ho and C. M. Wong, J. Chem. Soc. Chem. Comm., 1973, 224-225).

The following examples are intended to illustrate the invention, but notto limit the same in any way.

EXPERIMENTAL PART

NMR spectra were recorded on a JEOL FX-100 instrument as solutions inCDCl₃ with tetramethylsilane as internal standard.

IR spectra were measured with a Perkin-Elmer 225 Spectrophotometer, neator as solutions in CCl₄.

EXAMPLE 1 Preparation of Methylthiomethyl Hexanoate

In a three-necked 1000 ml. round-bottomed flask fitted with a mechanicalstirrer, thermometer and reflux condenser is placed 63.8 g. of hexanoicacid in 200 ml. of acetonitrile. To the stirred mixture is added, at20°-30° C., 55 g. of triethylamine over a period of 30 minutes. Thereaction mixture is stirred at room temperature for an additional 60minutes. Then is added, at 20°-24° C., 53 g. of chloromethyl methylsulfide in a few minutes. The reaction mixture is warmed and allowed toreflux for 24 hours. The reaction mixture is cooled to 5°-0° C. andfiltered. The solvent is stripped off under vacuum at 12 mm Hg pressure.The residue is taken up in diethyl ether and washed successively with a10% solution of sodium bicarbonate and with water. The organic layer isdried over anhydrous sodium sulfate. Distillation gives the title ester;b.p. 57°-58° C./2 mm Hg, n_(D) ²⁰ 1.4545.

Spectral data of the compound:

    ______________________________________                                        NMR SPECTRUM (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.88 (t, 3H)                                                                          2960, 2930, 2875, 2860, 1731(s),                            δ = 1-1.8 (-, 6H)                                                                         1470, 1417, 1220, 1162(s), 1106,                            δ = 2.23 (s, 3H)                                                                          1095, 964, 917, 750, 700 cm.sup.-1.                         δ = 2.33 (t, 2H)                                                        δ = 5.12 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 2 Preparation of Methylthiomethyl Formate

This product was prepared according to the procedure described inExample 1, by reacting formic acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 35° C./12 mm Hg,n_(D) ²⁰ 1.4650.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 2.26 (s, 3H)                                                                          2925, 1720, 1430, 1310, 1262,                               δ = 5.22 (s, 2H)                                                                          1130, 1010, 909, 870, 750, 694                              δ = 8.11 (t, 1H)                                                                          429 cm.sup.-1.                                              ______________________________________                                    

EXAMPLE 3 Preparation of Methylthiomethyl Acetate

This product was prepared according to the procedure described inExample 1, by reacting acetic acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 45°-46° C./12 mmHg, n_(D) ²⁰ 1.4570.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 2.07 (s, 3H)                                                                          2925, 1740(s), 1426, 1369, 1310,                            δ = 2.12 (s, 3H)                                                                          1210(s), 1018, 1008, 960, 910,                              δ = 5.10 (s, 2H)                                                                          812, 749, 697, 600, 462 cm.sup.-1.                          ______________________________________                                    

EXAMPLE 4 Preparation of Methylthiomethyl Propionate

This product was prepared according to the procedure described inExample 1, by reacting propionic acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 58°-59° C./12mm Hg, n_(D) ²⁰ 1.4548.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 1.15 (t, 3H)                                                                          2985, 2945, 2925, 1740, 1460,                               δ = 2.24 (s, 3H)                                                                          1423, 1356, 1263, 1160, 1078,                               δ = 2.36 (q, 2H)                                                                          995, 934, 805, 749, 696 cm.sup.-1.                          δ = 5.13 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 5 Preparation of Methylthiomethyl Butyrate

This product was prepared according to the procedure described inExample 1, by reacting butyric acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 71°-73° C./12 mmHg, n_(D) ²⁰ 1.4521.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.96 (t, 3H)                                                                          2970, 2940, 2880, 1740(s), 1460,                            δ = 1.66 (m, 2H)                                                                          1418, 1363, 1312, 1260, 1240,                               δ = 2.23 (s, 3H)                                                                          1156(s), 1098, 1080, 1035,                                  δ = 2.33 (t, 2H)                                                                          964(s), 920, 750, 696 cm.sup.-1.                            δ = 5.13 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 6 Preparation of Methylthiomethyl Isobutyrate

This product was prepared according to the procedure described inExample 1, by reacting isobutyric acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 64° C./12 mmHg, n_(D) ²⁰ 1.4470.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 1.19 (d, 6H)                                                                          2975, 2920, 2875, 1735(s), 1468,                            δ = 2.22 (s, 3H)                                                                          1424, 1385, 1358, 1234, 1181,                               δ = 2.56 (m, 1H)                                                                          1134(s), 1053, 1015, 957, 916,                              δ = 5.12 (s, 2H)                                                                          880, 800, 760, 696 cm.sup.-1.                               ______________________________________                                    

EXAMPLE 7

Preparation of Methylthiomethyl Valerate

This product was prepared according to the procedure described inExample 1, by reacting valeric acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 83°-85° C./12 mmHg, n_(D) ²⁰ 1.4560.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.92 (t, 3H)                                                                          2960, 2930, 2880, 1739(s), 1465,                            δ = 1-1.8 (m, 4H)                                                                         1416, 1260, 1225, 1150(s), 1103,                            δ = 2.22 (s, 3H)                                                                          1083, 960, 948, 746, 695 cm.sup.-1.                         δ = 2.32 (t, 2H)                                                        δ = 5.12 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 8 Preparation of Methylthiomethyl Isovalerate

This product was prepared according to the procedure described inExample 1, by reacting isovaleric acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 78°-79° C./12mm Hg, n_(D) ²⁰ 1.4496.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.92 (d, 6H)                                                                          2960, 2920, 2875, 1736(s), 1467,                            δ =  1.6 (m, 3H)                                                                          1425, 1366, 1310, 1284, 1237,                               δ = 2.21 (s, 3H)                                                                          1174, 1156(s), 1105, 1085, 975(s),                          δ = 5.12 (s, 2H)                                                                          940, 747, 693 cm.sup.-1.                                    ______________________________________                                    

EXAMPLE 9 Preparation of Methylthiomethyl 2-Methylbutyrate

This product was prepared according to the procedure described inExample 1, by reacting 2-methylbutyric acid with chloromethyl methylsulfide in the presence of one equivalent of triethylamine; b.p. 75°-77°C./12 mm Hg, n_(D) ²⁰ 1.4505.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.92 (t, 3H)                                                                          2985, 2930, 2875, 1736(s), 1460,                            δ = 1.16 (d, 3H)                                                                          1424, 1380, 1360, 1309, 1258,                               δ = 1.56 (m, 2H)                                                                          1220, 1170, 1133(s), 1064, 1000,                            δ = 2.23 (s, 3H)                                                                          966, 940, 756, 693 cm.sup.-1.                               δ = 2.40 (m, 1H)                                                        δ = 5.13 (s, 3H)                                                        ______________________________________                                    

EXAMPLE 10 Preparation of Methylthiomethyl Tiglate

This product was prepared according to the procedure described inExample 1, by reacting tiglic acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 95° C./12 mm Hg,n_(D) ²⁰ 1.4890.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                 IR spectrum (neat)                                            ______________________________________                                        δ = 0.80                                                                             d,           2980, 2920, 1710(s), 1647, 1430,                                 6H                                                               δ = 0.84                                                                             s,           1377, 1340, 1310, 1248(s), 1240(s)                  δ = 2.24                                                                             (s, 3H)      1140, 1116(s), 1080, 1060, 1014,                    δ = 5.20                                                                             (s, 2H)      961, 920, 745, 725 cm.sup.-1.                       δ = 6.80                                                                             (q, 1H)                                                          ______________________________________                                    

EXAMPLE 11 Preparation of Methylthiomethyl 2-Hexenoate

This product was prepared according to the procedure described inExample 1, by reacting 2-hexenoic acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 75°-76° C./2 mmHg, n_(D) ²⁰ 1.4836.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.94 (t, 3H)                                                                          2960, 2930, 2875, 1723, 1650,                               δ = 1.48 (m, 2H)                                                                          1424, 1333, 1313, 1237, 1158,                               δ = 2.2  (m, 2H)                                                                          1117, 1041, 984, 925, 750,                                  δ = 2.24 (s, 3H)                                                                          695 cm.sup.-1.                                              δ = 5.19 (s, 2H)                                                        δ = 5.84 (d, 1H)                                                        δ = 7.0  (m, 1H)                                                        ______________________________________                                    

EXAMPLE 12 Preparation of Methylthiomethyl 2-Methyl-2-pentenoate

This product was prepared according to the procedure described inExample 1, by reacting 2-methyl-2-pentenoic acid with chloromethylmethyl sulfide in the presence of one equivalent of triethylamine; b.p.56°-57° C./2 mm Hg, n_(D) ²⁰ 1.4861.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 1.05 (t, 3H)                                                                          2965, 2930, 2875, 1720, 1649,                               δ = 1.84 (s, 3H)                                                                          1439, 1334, 1314, 1263, 1233,                               δ = 2.2  (m, 2H)                                                                          1154, 1132, 1095, 1076, 990,                                δ = 2.24 (s, 3H)                                                                          940, 750 cm.sup.-1.                                         δ = 5.20 (s, 2H)                                                        δ = 6.81 (t, 1H)                                                        ______________________________________                                    

EXAMPLE 13 Preparation of Methylthiomethyl Heptanoate

This product was prepared according to the procedure described inExample 1, by reacting heptanoic acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 80°-81° C./2 mmHg, n_(D) ²⁰ 1.4591.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.89 (t, 3H)                                                                          2960, 2925, 2860, 1740(s), 1466,                            δ = 1-1.8 (-, 8H)                                                                         1455, 1415, 1360, 1330, 1310,                               δ = 2.23 (s, 3H)                                                                          1260, 1220, 1145(s), 1100, 973,                             δ = 2.35 (t, 2H)                                                                          956, 746, 723, 695 cm.sup.-1.                               δ = 5.12 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 14 Preparation of Methylthiomethyl Octanoate

This product was prepared according to the procedure described inExample 1, by reacting octanoic acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 90° C./2 mm Hg,n_(D) ²⁰ 1.4577.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.88 (t, 3H)                                                                          2955, 2920, 2860, 1734(s), 1460,                            δ = 1-1.8 (-, 10H)                                                                        1409, 1370, 1327, 1305, 1254,                               δ = 2.23 (s, 3H)                                                                          1210, 1140(s), 1100, 960, 742,                              δ = 2.34 (t, 2H)                                                                          716, 692 cm.sup.-1.                                         δ = 5.12 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 15 Preparation of Methylthiomethyl Citronellate

This product was prepared according to the procedure described inExample 1, by reacting citronellic acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 110° C./2 mmHg, n_(D) ²⁰ 1,4760.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 0.96 (d, 3H)                                                                          2960, 2920, 2855, 1740(s), 1434,                            δ = 1.58 (s, 3H)                                                                          1374, 1330, 1310, 1280, 1216,                               δ = 1.67 (s, 3H)                                                                          1170, 1130, 1072, 970, 746,                                 δ = 2.12 (s, 3H)                                                                          692 cm.sup.-1.                                              δ = 5.10 (s, 2H)                                                        ______________________________________                                    

EXAMPLE 16 Preparation of Methylthiomethyl Geranate

This product was prepared according to the procedure described inExample 1, by reacting geranic acid with chloromethyl methyl sulfide inthe presence of one equivalent of triethylamine; b.p. 111°-112° C./2 mmHg, n²⁰ 1.4912.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                   IR spectrum (neat)                                          ______________________________________                                        δ = 1.62 (s, 3H)                                                                          2965, 2920, 2855, 1720(s), 1641,                            δ = 1.70 (s, 3H)                                                                          1435, 1373, 1356, 1210, 1125(s),                            δ = 2.18 (-, 7H)                                                                          1050, 974, 929, 860, 815, 748,                              δ = 2.24 (s, 3H)                                                                          693 cm.sup.-1.                                              δ = 5.08 (-, 1H)                                                        δ = 5.16 (s, 2H)                                                        δ = 5.70 (s, 1H)                                                        ______________________________________                                    

EXAMPLE 17 Preparation of Methylthiomethyl Lavandulate

This product was prepared according to the procedure described inExample 1, by reacting lavandulic acid with chloromethyl methyl sulfidein the presence of one equivalent of triethylamine; b.p. 93°-94° C./2 mmHg, n²⁰ 1.4855.

Spectral data of the compound:

    ______________________________________                                        NMR spectrum (δ in ppm)                                                                 Ir spectrum (neat)                                            ______________________________________                                        δ = 1.63                                                                             s            3080, 2970, 2925, 1738(s), 1644,                    δ = 1.67                                                                             s, 9H        1435, 1384, 1340, 1255, 1166,                       δ = 1.78                                                                             s            1130(s), 984, 965, 925, 895,                        δ = 2.20                                                                             (s, 3H)      770, 744, 694 cm.sup.-1.                            δ = 3.06                                                                             (t, 3H)                                                          δ = 5.12                                                                             (s, 2H)                                                          ______________________________________                                    

EXAMPLE 18

Two cheese flavor enhancing compositions were prepared by mixing thefollowing ingredients:

    ______________________________________                                                          A      B                                                    ______________________________________                                        butyric acid        30        30                                              hexanoic acid       3        3                                                isovaleric acid     3        3                                                octanoic acid       5        5                                                2-heptanone         2        2                                                γ-undecalactone                                                                             0.5      0.5                                              ethyl lactate       10       10                                               γ-decalactone 0.5      0.5                                              γ-dodecalactone                                                                             0.5      0.5                                              acetoin             0.2      0.2                                              diacetyl            0.1      0.1                                              methylcinnamate     0.5      0.5                                              methylthiomethyl hexanoate                                                                        --       0.5                                              propylene glycol    944.7     944.2                                                               1000.0   1000.0                                           ______________________________________                                    

Mixtures A and B were added separately to a commercially available lowcaloric processed cheese (20% fat content) at a level of 4 g. perkilogram. The processed cheese containing mixture A was compared withthe processed cheese containing mixture B. The processed cheesecontaining mixture B was preferred over the processed cheese containingmixture A, because it had a more pronounced cheese taste with anincreased creamy character.

EXAMPLE 19

Three pineapple flavor compositions were prepared by mixing thefollowing ingredients:

    ______________________________________                                                       A      B        C                                              ______________________________________                                        vanillin         16       16       16                                         maltol           16       16       16                                         benzylalcohol    80       80       80                                         linalool         8        8        8                                          isoamyl butyrate 24       24       24                                         ethyl acetate    32       32       32                                         ethyl butyrate   32       32       32                                         ethyl hexanoate  64       64       64                                         ethyl heptanoate 48       48       48                                         methylthiomethyl octanoate                                                                     --       2.5      --                                         methylthiomethyl heptanoate                                                                    --       --        2.5                                       propylene glycol  680     677.5     677.5                                                      1000.0   1000.0   1000.0                                     ______________________________________                                    

Mixtures A, B and C were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.1 g. per liter. Theflavored solutions were tasted and compared. As compared with mixture A,the taste of mixture B is preferred because it is more pineapple-likewith a more natural taste and aftertaste. As compared with mixture A,the taste of mixture C is preferred because it has a better pineapplecharacter with increased fruitiness and the heavy natural sweetness ofthe genuine fruit.

EXAMPLE 20

Two strawberry flavor compositions were prepared by mixing the followingingredients:

    ______________________________________                                                          A      B                                                    ______________________________________                                        maltol              30        30                                              cis-3-hexenol       0.6      0.6                                              ethyl isovalerate   1        1                                                γ-undecalactone                                                                             3        3                                                benzyl butyrate     3        3                                                ethyl butyrate      20       20                                               ethyl acetate       1        1                                                amyl acetate        1        1                                                geranyl acetate     0.1      0.1                                              diacetyl            0.1      0.1                                              γ-nonalactone 0.1      0.1                                              β-terpineol    0.08     0.08                                             Ylang Ylang oil     0.02     0.02                                             Orange oil          0.3      0.3                                              phenylethyl isovalerate                                                                           2.2      2.2                                              methylthiomethyl isobutyrate                                                                      --       2.5                                              propylene glycol    937.50    935.00                                                              1000.00  1000.00                                          ______________________________________                                    

Mixtures A and B were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. Theflavored test solutions were compared. The test solution containingmixture B was preferred over the test solution containing mixture Abecause it has an improved strawberry character with notes reminiscentof a ripe, jammy strawberry. Similar notes were not found in the testsolution containing mixture A.

EXAMPLE 21

Three cream flavor compositions were prepared by mixing the followingingredients:

    ______________________________________                                                        A      B        C                                             ______________________________________                                        acetoin           30       30       30                                        diacetyl          20       20       20                                        vanillin          20       20       20                                        ethyl butyrate    10       10       10                                        maltol            5        5        5                                         δ-decalactone                                                                             10       10       10                                        ethyl lactate     50       50       50                                        butyric acid      50       50       50                                        hexanoic acid     5        5        5                                         methylthiomethyl propionate                                                                     --       2.5      --                                        methylthiomethyl butyrate                                                                       --       --       0.5                                       propylene glycol  800      797.5    799.5                                                       1000.0   1000.0   1000.0                                    ______________________________________                                    

Mixtures A, B and C were added separately to a test solution (containing8% sugar) at a level of 0.2 g. per liter. The flavored solutions weretasted and compared. As compared with mixture A, the taste of mixture Bis more pronounced cream-like, having an improved dairy character. Thetest solution containing mixture B was therefore preferred over the testsolution containing mixture A. As compared to mixture A, the taste ofmixture C is preferred because it showed a fuller, richer, morecream-like character, with enhanced sweet notes.

EXAMPLE 22

Two mango flavor compositions were prepared by mixing the followingingredients:

    ______________________________________                                                         A      B                                                     ______________________________________                                        ethylmaltol        20        20                                               vanillin           4.5      4.5                                               isopropyl alcohol  300      300                                               mandarin oil       5        5                                                 ethyl acetate      3        3                                                 orange essence oil 4        4                                                 2-methylbutyric acid                                                                             3.5      3.5                                               cis-3-hexenol      5.5      5.5                                               γ-undecalactone                                                                            1        1                                                 propylene glycol   653.5    646                                               methylthiomethyl-2-methylbutyrate                                                                --       7.5                                                                  1000.0   1000.0                                            ______________________________________                                    

Mixtures A and B were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. Theflavored solutions were tasted and compared. As compared with mixture A,the taste of mixture B is more mango-like with a typical sulfury,fruity, tropical note which is important for this fruit. Since this notewas not found in the test solution containing mixture A, the testsolution containing mixture B was preferred.

EXAMPLE 23

Three blackcurrant flavor compositions were prepared by mixing thefollowing ingredients:

    ______________________________________                                                        A      B        C                                             ______________________________________                                        vanillin          4        4        4                                         angelicaroot oil  6        6        6                                         buchu oil         100      100      100                                       cognac oil (green)                                                                              3        3        3                                         mandarin oil      4        4        4                                         petitgrain oil    10       10       10                                        cedar leaf oil    3        3        3                                         isoamyl isovalerate                                                                             15       15       15                                        isoamyl butyrate  4        4        4                                         methyl butyrate   20       20       20                                        ethyl butyrate    10       10       10                                        ethyl hexanoate   5        5        5                                         isobutyl acetate  120      120      120                                       methyl isobutyl carbinylacetate                                                                 20       20       20                                        ethylbenzoate     5        5        5                                         bornyl acetate    8        8        8                                         citral            2        2        2                                         cuminic aldehyde  3        3        3                                         β-ionone     3        3        3                                         methylthiomethyl valerate                                                                       --       10       --                                        methylthiomethyl tiglate                                                                        --       --       10                                        propylene glycol  655      645      645                                                         1000.0   1000.0   1000.0                                    ______________________________________                                    

Mixtures A, B and C were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.01 g. per liter. Theflavored solutions were tasted and compared. As compared with mixture A,the taste of mixture B is preferred because it has a better blackcurrantflavor with a fresh, fruity topnote reminiscent of the fresh fruit. Ascompared with mixture A, the taste of mixture C is preferred because ithas a blackcurrant flavor with increased sweet body notes giving aricher fuller fruity character.

EXAMPLE 24

Two peach flavor compositions were prepared by mixing the followingingredients:

    ______________________________________                                                           A      B                                                   ______________________________________                                        vanillin             4.5      4.5                                             ethylmaltol          20       20                                              tangerine oil        5        5                                               ethyl acetate        3        3                                               benzyl acetate       3        3                                               orange peel oil      4        4                                               bergamot oil         1        1                                               2-methylbutyric acid 3.5      3.5                                             cis-3-hexenol        5.5      5.5                                             benzyl alcohol       15       15                                              methylthiomethyl isovalerate                                                                       --       5                                               propylene glycol     935.5    930.5                                                                1000.0   1000.0                                          ______________________________________                                    

Mixtures A and B were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. Theflavored solutions were tasted and compared. As compared with mixture A,the taste of mixture B is preferred because it has a better peachcharacter with improved aftertaste and a sweet jammy note reminiscent ofripe peach.

EXAMPLE 25

Two condensed milk flavor compositions were prepared by mixing thefollowing ingredients:

    ______________________________________                                                          A      B                                                    ______________________________________                                        heliotropin         1        1                                                vanillin            20       20                                               maltol              5        5                                                acetoin             40       40                                               diacetyl            20       20                                               ethyl butyrate      8        8                                                ethyl hexanoate     2        2                                                δ-decalactone 10       10                                               γ-nonalactone 1        1                                                n-butyric acid      40       40                                               hexanoic acid       4        4                                                methylthiomethyl 2-hexenoate                                                                      --       5                                                propylene glycol    849      844                                                                  1000.0   1000.0                                           ______________________________________                                    

Mixtures A and B were added separately to a test solution (containing 8%sugar) at a level of 0.2 g. per liter. The flavored solutions weretasted and compared. As compared with mixture A, the taste of mixture Bis preferred because it has a pronounced cooked milk character with aricher creamier aftertaste.

EXAMPLE 26

Two grape flavor compositions were prepared by mixing the followingingredients:

    ______________________________________                                                          A      B                                                    ______________________________________                                        maltol              0.25     0.25                                             cognac oil (green)  0.1      0.1                                              lime oil            0.4      0.4                                              orange oil terpenes 0.8      0.8                                              isoamyl acetate     0.3      0.3                                              fusel oil           2        2                                                ethyl acetate       2        2                                                ethyl butyrate      0.4      0.4                                              lie de vin          0.1      0.1                                              ethyl 2-methylbutyrate                                                                            0.3      0.3                                              2-methylbutanol     2        2                                                citral              0.05     0.05                                             phenylethyl alcohol 0.25     0.25                                             trans-2-hexenol     0.1      0.1                                              methyl anthranilate 10       6                                                methylthiomethyl lavandulate                                                                      --       4                                                propylene glycol    980.95   980.95                                                               1000.0   1000.0                                           ______________________________________                                    

Mixtures A and B were added separately to a test solution (containing10% sugar and 0.05% citric acid) at a level of 0.2 g. per liter. Theflavored solutions were tasted and compared. As compared with mixture A,the taste of mixture B is preferred because it has an improved grapecharacter with a more natural aftertaste and does not have the harshmethyl anthranilate taste shown by mixture A.

What we claim and desire to protect by Letters Patent is:
 1. A fruit orberry flavoring composition or a fruit or berry flavor-enhancingcomposition comprising a combination of olfactorily active ingredientsincluding at least one methylthiomethyl ester having the structuralformula R--COOCH₂ --S--CH₃ wherein R is selected from the classconsisting of hydrogen, alkyl radicals with 2 to 9 carbon atoms, alkenylradicals with 2 to 9 carbon atoms, and polyunsaturated radicals with 4to 9 carbon atoms and at least one compound selected from the classconsisting of:orange oil isoamyl acetate phenyl ethyl isovalerate fuseloil damascenone lie de vin ethyl maltol 2-methyl butanol 2-methylbutyricacid phenylethyl alcohol angelica root oil trans-2-hexenol buchu oilmethyl anthranilate cognac oil 2-methyl-2-pentenoic acid petitgrain oilvanillin cedar leaf oil maltol isoamyl isovalerate benzyl alcohol methylbutyrate linaolool isobutyl acetate isoamyl butyrate methyl isobutylcarbinyl acetate ethyl acetate ethyl butyrate ethyl benzoate ethylhexanoate citral ethyl heptanoate cuminic aldehyde cis-3-hexenolbeta-ionone ethyl isovalerate tangerine oil phenyl butyrate benzylacetate amyl acetate orange peel oil geranyl acetate bergamot oilgamma-nonalactone lime oil Ylang Ylang orange terpenes beta-terpineolmethyl cinnamate.
 2. A flavoring composition according to claim 1wherein R is hydrogen or an alkyl radical with 1 to 9 carbon atoms. 3.The flavoring composition according to claim 2 wherein the ester ismethylthiomethyl butyrate.
 4. The flavoring composition according toclaim 2 wherein the ester is methylthiomethyl isobutyrate.
 5. Theflavoring composition according to claim 2 wherein the ester ismethylthiomethyl 2-methylbutyrate.
 6. The flavoring compositionaccording to claim 2 wherein the ester is methylthiomethyl valerate. 7.The flavoring composition according to claim 2 wherein the ester ismethylthiomethyl isovalerate.
 8. The flavoring composition according toclaim 2 wherein the ester is methylthiomethyl hexanoate.
 9. Theflavoring composition according to claim 2 wherein the ester ismethylthiomethyl heptanoate.
 10. The flavoring composition according toclaim 2 wherein the ester is methylthiomethyl octanoate.
 11. A flavoringcomposition according to claim 1 wherein R is an alkenyl radical with 2to 9 carbon atoms.
 12. The flavoring composition according to claim 11wherein the ester is methylthiomethyl tiglate.
 13. The flavoringcomposition according to claim 11 wherein the ester is methylthiomethyl2-hexenoate.
 14. The flavoring composition according to claim 11 whereinthe ester is methylthiomethyl 2-methyl-2-pentenoate.
 15. A flavoringcomposition according to claim 1 wherein R is a polyunsaturated alkylradical with 4 to 9 carbon atoms.
 16. The flavoring compositionaccording to claim 15 wherein the ester is methylthiomethyl lavandulate.17. A foodstuff to which has been added about 0.1 to 5 parts permillion, based on the total weight of said foodstuff, of at least onemethylthiomethyl ester having the structural formula R--COOCH₂ SCH₃wherein R is selected from the class consisting of hydrogen, alkylradicals with 1 to 9 carbon atoms, alkenyl radicals with 2 to 9 carbonatoms and polyunsaturated alkyl radicals with 4 to 9 carbon atoms.
 18. Afoodstuff according to claim 17 wherein R is hydrogen or an alkylradical with 1 to 9 carbon atoms.
 19. The foodstuff of claim 18 whereinthe ester is methylthiomethyl butyrate.
 20. The foodstuff of claim 18wherein the ester is methylthiomethyl isobutyrate.
 21. The foodstuff ofclaim 18 wherein the ester is methylthiomethyl 2-methylbutyrate.
 22. Thefoodstuff of claim 18 wherein the ester is methylthiomethyl valerate.23. The foodstuff of claim 18 wherein the ester is methylthiomethylisovalerate.
 24. The foodstuff of claim 18 wherein the ester ismethylthiomethyl hexanoate.
 25. The foodstuff of claim 18 wherein theester is methylthiomethyl heptanoate.
 26. The foodstuff of claim 18wherein the ester is methylthiomethyl octanoate.
 27. A foodstuffaccording to claim 17 wherein R is an alkenyl radical with 2 to 9 carbonatoms.
 28. The foodstuff of claim 27 wherein the ester ismethylthiomethyl tiglate.
 29. The foodstuff of claim 27 wherein theester is methylthiomethyl 2-hexenoate.
 30. The foodstuff of claim 27wherein the ester is methylthiomethyl 2-methyl-2-pentenoate.
 31. Afoodstuff according to claim 17 wherein R is a polyunsaturated alkylradical with 4 to 9 carbon atoms.
 32. The foodstuff of claim 31 whereinthe ester is methylthiomethyl lavandulate.
 33. A method of improving theflavor of a foodstuff which comprises adding thereto about 0.1 to 5parts per million of at least one methylthiomethyl ester having thestructural formula R--COOCH₂ SCH₃ wherein R is selected from the classconsisting of hydrogen, alkyl radicals with 1 to 9 carbon atoms, alkenylradicals with 2 to 9 carbon atoms and polyunsaturated alkyl radicalswith 4 to 9 carbon atoms.